CHAPTER 24

COMPLEX IONS AND COORDINATION COMPOUNDS

PRACTICE EXAMPLES
1A

1B
2A

There are two different kinds of ligands in this complex ion, I and CN. Both are
monodentate ligands, that is, they each form only one bond to the central atom. Since there
are five ligands in total for the complex ion, the coordination number is 5: C.N. = 5 . Each
CN ligand has a charge of 1, as does the I ligand. Thus, the O.S. must be such that:
O.S. + 4 +1 1 = 3 = O.S. 5 . Therefore, O.S. = +2 .
The ligands are all CN . Fe3+ is the central metal ion. The complex ion is Fe CN 6 .
3

There are six Cl ligands (chloride), each with a charge of 1. The platinum metal center
2
has an oxidation state of +4 . Thus, the complex ion is PtCl6 , and we need two K + to

balance charge: K 2 PtCl6 .

2B

The SCN ligand is the thiocyanato group, with a charge of 1bonding to the central
metal ion through the sulfur atom. The NH3 ligand is ammonia, a neutral ligand. There
are five (penta) ammine ligands bonded to the metal. The oxidation state of the cobalt atom
is +3 . The complex ion is not negatively charged, so its name does not end with -ate.
The name of the compound is pentaamminethiocyanato-S-cobalt(III) chloride.

3A

The oxalato ligand must occupy two cis- positions. Either the two NH3 or the two Cl
ligands can be coplanar with the oxalate ligand, leaving the other two ligands axial. The
other isomer has one NH3 and one Cl ligand coplanar with the oxalate ligand. The
structures are sketched below.

ox
Cl
3B

Cl
Co NH3
NH3

ox
H3N

NH3
Co Cl
Cl

ox
H3N

Cl
Co NH3
Cl

We start out with the two pyridines, C5 H 5 N , located cis to each other. With this assignment
imposed, we can have the two Clligands trans and the two CO ligands cis, the two CO
ligands trans and the two Cl ligands cis, or both the Clligands and the two CO ligands cis.
If we now place the two pyridines trans, we can have either both other pairs trans, or both
other pairs cis. There are five geometric isomers. They follow, in the order described.

647

Chapter 24: Complex Ions and Coordination Compounds

4A

The F ligand is a weak field ligand. MnF6

is an octahedral complex. Mn 4+ has three

2

3d electrons. The ligand field splitting diagram for MnF6 is sketched below. There are

three unpaired electrons.

eg

t2g
4B

Co2+ has seven 3d electrons. Cl is a weak field ligand. H2O is a moderate field ligand.
There are three unpaired electrons in each case. The number of unpaired electrons has no
dependence on geometry for either metal ion complex.

CoCl

Co H 2O 6

5A

2+

CN is a strong field ligand. Co 2+ has seven 3d electrons. In the absence of a crystal field,
all five d orbitals have the same energy. Three of the seven d electrons in this case will be
unpaired. We need an orbital splitting diagram in which there are three orbitals of the
same energy at higher energy. This is the case with a tetrahedral orbital diagram.

t2 g

eg

In absence of a
crystal field

eg

t2 g

Tetrahedral geometry

Octahedralgeometry

Thus, Co CN 4 must be tetrahedral (3 unpaired electrons) and not octahedral (1

unpaired electron) because the magnetic behavior of a tetrahedral arrangement would
agree with the experimental observations (3 unpaired electrons).
2

5B

NH3 is a strong field ligand. Cu 2+ has nine 3d electrons. There is only one way to arrange
nine electrons in five d-orbitals and that is to have four fully occupied orbitals (two
electrons in each orbital), and one half-filled orbital. Thus, the complex ion must be
paramagnetic to the extent of one unpaired electron, regardless of the geometry the ligands
adopt around the central metal ion.

6A

We are certain that Co H 2O 6

CoCl

is octahedral with a moderate field ligand. Tetrahedral

has a weak field ligand. The relative values of ligand field splitting for the same

ligand are t = 0.44 o . Thus, Co H 2O 6

648

2+

absorbs light of higher energy, blue or

Chapter 24: Complex Ions and Coordination Compounds

green light, leaving a light pink as the complementary color we observe. CoCl 4
absorbs lower energy red light, leaving blue light to pass through and be seen.

CO

NC5H5
Cl Mo Cl
OC
NC5H5

6B

Cl

NC5H5
OC Mo CO
Cl
NC5H5

Cl

NC5H5
CO
Cl Mo Cl
OC
NC5H5

NC5H5
Cl Mo CO
OC
NC5H5

NC5H5
CO
Cl Mo CO
Cl
NC5H5

In order, the two complex ions are Fe H 2O 6 and Fe CN 6 . We know that CN

is a strong field ligand; it should give rise to a large value of o and absorb light of the
4

2+

shorter wavelength. We would expect the cyano complex to absorb blue or violet light and
thus K 4 Fe CN 6 3 H 2O should appear yellow. The compound Fe H 2O 6 NO 3 2 ,
contains the weak field ligand H2O and thus should be green. (The weak field would result
in the absorption of light of long wavelength (namely, red light), which would leave green
as the color we observe.)

INTEGRATIVE EXAMPLE
A

(a) There is no reaction with AgNO3 or en, so the compound must be transchlorobis(ethylenediamine)nitrito-N-cobalt(III) nitrite
+
H2
N

Cl

H2
N

Co
H2N
NO2

NO2-

N
H2

(b) If the compound reacts with AgNO3, but not with en, it must be transbis(ethylenediamine)dinitrito-N-cobalt(III) chloride.
+
H
N

NO2

H
N

Co
HN
NO2

Cl-

N
H

(c) If it reacts with AgNO3 and en and is optically active, it must be cisbis(ethylenediamine)dinitrito-N-cobalt(III) chloride.

649

Chapter 24: Complex Ions and Coordination Compounds

+
H2
N

NO2

H2
N

Co
H2N
NO2

Cl-

N
H2

We first need to compute the empirical formula of the complex compound:

0.236
1 mol Pt
=0.236 mol Pt
=1 mol Pt
46.2 g Pt
0.236
195.1 g Pt
0.946
1 mol Cl
=0.946 mol Cl
=4 mol Pt
33.6 g Cl
0.236
35.5 g Cl
1.18
1 mol N
=1.18 mol N
=5 mol N
16.6 g N
0.236
14.01 g N
3.6
1 mol H
=3.6 mol H
=15 mol H
3.6 g Pt
0.236
1gH
The nitrogen ligand is NH3, apparently, so the empirical formula is Pt(NH3)5Cl4.
T
0.74 o C
The effective molality of the solution is m

0.4m . The effective

K fp 1.86 o C / m
molality is 4 times the stated molality, so we have 4 particles produced per mole of Pt
complex, and therefore 3 ionizable chloride ions. We can write this in the following way:
[Pt(NH3)5Cl][Cl]3. Only one form of the cation (with charge 3+) shown below will exist.
+3
NH3
H3N

NH3
Pt

H3N

NH3
Cl

EXERCISES
Nomenclature
1.

(a)

CrCl4 NH 3 2

(b)

Fe CN 6

(c)

diamminetetrachlorochromate(III) ion
hexacyanoferrate(III) ion

Cr en 3 Ni CN 4 . tris(ethylenediamine)chromium(III) tetracyanonickelate(II)
3
2
ion
650

Chapter 24: Complex Ions and Coordination Compounds

3.

(a)

Co OH H 2 O 4 NH 3

(b)

Co ONO 3 NH 3 3

triamminetrinitrito-O-cobalt(III)

(c)

Pt H 2O 4 PtCl6

tetraaquaplatinum(II) hexachloroplatinate(IV)

(d)

Fe ox 2 H 2O 2

diaquadioxalatoferrate(III) ion

(e)

Ag 2 HgI 4

2+

amminetetraaquahydroxocobalt(III) ion

silver(I) tetraiodomercurate(II)

Bonding and Structure in Complex Ions

5.

The Lewis structures are grouped together at the end.

(a)

H2O has 12 + 6 = 8 valence electrons, or 4 pairs.

(b)

CH 3 NH 2 has 4 + 3 1+ 5 + 2 1 = 14 valence electrons, or 7 pairs.

(c)

ONO has 2 6 + 5 +1 = 18 valence electrons, or 9 pairs. The structure has a 1

formal charge on the oxygen that is singly bonded to N.

(d)

SCN has 6 + 4 + 5 +1 = 16 valence electrons, or 8 pairs. This structure,

appropriately, gives a 1 formal charge to N.
H H
H
N C H
O N O
S C N
O
H
H H
(a)

7.

(b)

(c)

(d)

is square planar by analogy with PtCl2 NH 3 2 in Figure 245. The other two complex ions are octahedral.
We assume that PtCl 4

(a)

2-

Cl
Cl

Pt

Cl

(b)
H2O
H2O

Cl

651

2+
NH3
NH3
Co NH3
OH2

(c)

Cl

OH2
H2O Cr OH2
H2O
OH2

2+

Chapter 24: Complex Ions and Coordination Compounds

9.

NH3
NH3

(a)
H3N

Cr

H3N

3-

(b)

OSO 3

C C

O Co O
C O
C O
O C
O
O

O C

NH3

pentaamminesulfateochromium(III)

trioxalatocobaltate(III)

(c)
fac-triamminedichloronitro-O-cobalt(III)
NH3
NH3
Cl
Co NH3
ONO

mer-triammine-cis-dichloronitro-O-cobalt(III)
NH3
NH3
Cl Co ONO
Cl

Cl

NH3

mer-triammine-trans-dichloronitro-O-cobalt(III)
NH3
NH3
Cl Co Cl
ONO

NH3

Isomerism
11.

(a)

cis-trans isomerism cannot occur with tetrahedral structures because all of the
ligands are separated by the same angular distance from each other. One ligand
cannot be on the other side of the central atom from another.

(b)

Square planar structures can show cis-trans isomerism. Examples are drawn following,
with the cis-isomer drawn on the left, and the trans-isomer drawn on the right.
A
A
B
B

(c)

A
B
cis-isomer

B
A
trans-isomer

Linear structures do not display cis-trans isomerism; there is only one way to bond
the two ligands to the central atom.

652

Chapter 24: Complex Ions and Coordination Compounds

13.

(a) There are three different square planar isomers, with D, C, and B, respectively, trans
to the A ligand. They are drawn below.
B

A
Pt
C

(b)

15.

A
Pt

2+

Zn

Tetrahedral ZnABCD
are drawn above.

Pt
C

Zn
D

does display optical isomerism. The two optical isomers

The cis-dichlorobis(ethylenediamine)cobalt(III) ion is optically active. The two optical

isomers are drawn below. The trans-isomer is not optically active: the ion and its mirror
image are superimposable.
Cl

Cl
Cl

Cl

N Co N N
C
N
C C
C
C
N C
cis-isomers

Co N
C
N
C
N

C N
C

Cl
Co

Cl

C
N C
trans-isomer

Crystal Field Theory

17.

In crystal field theory, the five d orbitals of a central transition metal ion are split into two
(or more) groups of different energies. The energy spacing between these groups often
corresponds to the energy of a photon of visible light. Thus, the transition-metal complex
will absorb light with energy corresponding to this spacing. If white light is incident on the
complex ion, the light remaining after absorption will be missing some of its components.
Thus, light of certain wavelengths (corresponding to the energies absorbed) will no longer
be present in the formerly white light. The resulting light is colored. For example, if blue
light is absorbed from white light, the remaining light will be yellow in color.

19. We begin with the 7 electron d-orbital diagram for Co2+ [Ar]
The strong field and weak field diagrams for octahedral complexes follow, along with the
number of unpaired electrons in each case.

Strong Field

(1 unpaired
electron)

Weak Field

eg

eg

(3 unpaired
electrons)

t2g

653

t2g

Chapter 24: Complex Ions and Coordination Compounds

21.

(a)

Both of the central atoms have the same oxidation state, +3. We give the electron
configuration of the central atom to the left, then the completed crystal field diagram
in the center, and finally the number of unpaired electrons. The chloro ligand is a
weak field ligand in the spectrochemical series.
Mo 3+

eg

Kr 4d 3

weak field

Kr

t2g
3 unpaired electrons; paramagnetic

4d

The ethylenediamine ligand is a strong field ligand in the spectrochemical series.

Co 3+

Ar 3d 6

eg

strong field

Ar

t2g
no unpaired electrons; diamagnetic

(b)

In CoCl 4 the oxidation state of cobalt is 2+. Chloro is a weak field ligand. The
electron configuration of Co 2+ is Ar 3d 7 or Ar
The tetrahedral ligand field diagram is
shown on the right.

weak field

t2g
eg

3 unpaired electrons

23. The electron configuration of Ni 2+ is Ar 3d 8 or Ar

Ammonia is a strong field ligand. The ligand field diagrams follow, octahedral at left,
tetrahedral in the center and square planar at right.
Octahedral
eg
t2g

Tetrahedral

Square Planar

t2g

dx2-y2
dxy
dz2
dxz, dyz

eg

Since the octahedral and tetrahedral configurations have the same number of unpaired
electrons (that is, 2 unpaired electrons), we cannot use magnetic behavior to determine
whether the ammine complex of nickel(II) is octahedral or tetrahedral. But we can
determine if the complex is square planar, since the square planar complex is diamagnetic
with zero unpaired electrons.

654

Chapter 24: Complex Ions and Coordination Compounds

Complex-Ion Equilibria
25. (a)

Zn NH3
Zn OH 2 s + 4 NH 3 aq

aq + 2 OH aq

2+

Cu OH s
Cu 2+ aq + 2 OH aq
2

(b)

The blue color is most likely due to the presence of some unreacted [Cu(H2O)4]2+ (pale blue)
Cu NH 3
Cu OH 2 s + 4 NH 3 aq

Cu NH 3 4
27.

29.

2+

2+

aq,

dark blue + 2 OH aq

Cu H 2 O aq + 4 NH 4 + aq
aq + 4 H3O+ aq

4
2+

Co en 3 should have the largest overall Kf value. We expect a complex ion with
polydentate ligands to have a larger value for its formation constant than complexes that
contain only monodentate ligands. This phenomenon is known as the chelate effect. Once
one end of a polydentate ligand becomes attached to the central metal, the attachment of
the remaining electron pairs is relatively easy because they already are close to the central
metal (and do not have to migrate in from a distant point in the solution).
3+

First: Fe H 2 O 6

3+

Fe H 2 O en aq + 2H 2 O(l)
aq + en aq
4

3+

Second: Fe H 2 O 4 en
Third:

3+

Fe H 2 O 2 en 2

aq +

3+

en aq Fe H 2O 2 en 2

aq +

en aq Fe en 3

3+

3+

K1 = 104.34

aq + 2H 2 O(l)

aq + 2H 2O(l)

K2 = 103.31

K3 = 102.05

Fe H 2 O 6 aq + 3 en aq Fe en 3 aq + 6H 2 O(l)
K f = K1 K2 K3
log Kf = 4.34 + 3.31+ 2.05 = 9.70
Kf = 109.70 = 5.0 109 = 3

Net:

31.

(a)

3+

3+

Aluminum(III) forms a stable (and soluble) hydroxo complex but not a stable
ammine complex.

Al H 2 O OH aq + H 2 O(l)
Al H 2 O 3 OH 3 s + OH aq
2
4

(b)

Although zinc(II) forms a soluble stable ammine complex ion, its formation constant
is not sufficiently large to dissolve highly insoluble ZnS. However, it is sufficiently
large to dissolve the moderately insoluble ZnCO 3 . Said another way, ZnS does not
produce sufficient Zn 2+ to permit the complex ion to form.

Zn NH 3
ZnCO3 s + 4 NH 3 aq
4

655

2+

aq + CO32 aq

Chapter 24: Complex Ions and Coordination Compounds

(c)

Chloride ion forms a stable complex ion with silver(I) ion, that dissolves the AgCl(s)
that formed when Cl is low.

AgCl s Ag + aq + Cl aq

and

Ag + aq + 2 Cl aq AgCl2 aq

AgCl2 aq
Overall: AgCl s + Cl aq

Acid-Base Properties
33.

Al H 2O 6

3+

aq is capable of releasing H+:

Al H 2 O 6

3+

AlOH H 2 O aq + H 3O + aq
aq + H 2O(l)
5

2+

The value of its ionization constant ( pKa = 5.01) approximates that of acetic acid.

Applications
35.

(a)

Solubility:
Cplx. Ion Formation:

K =5.01013

sp
+

AgBr s
Ag aq + Br aq
f

Ag + aq + 2S2 O32 aq
Ag S2 O3 2

K =1.71013

Ag S2 O3
Net: AgBr s + 2S2 O32 aq

aq +

Br - (aq)

aq

K overall = K sp K f

K overall = 5.0 1013 1.7 1013 = 8.5

With a reasonably high S2 O 3
(b)

, this reaction will go essentially to completion.

NH 3 aq cannot be used in the fixing of photographic film because of the relatively

small value of Kf for Ag NH 3 2 aq , Kf = 1.6 107 . This would produce a
value of K = 8.0 106 in the expression above, which is nowhere large enough to
drive the reaction to completion.
+

37.

To make the cis isomer, we must use ligands that show a strong tendency for
directing incoming ligands to positions that are trans to themselves. I has a stronger
tendency than does Cl or NH3 for directing incoming ligands to the trans positions, and
so it is beneficial to convert K2[PtCl4] to K2[PtI4] before replacing ligands around Pt with
NH3 molecules.

656

Chapter 24: Complex Ions and Coordination Compounds

INTEGRATIVE AND ADVANCED EXERCISES

39.
(a)
(b)
(c)
(d)
(e)

cupric tetraammine ion

dichlorotetraamminecobaltic chloride
platinic(IV) hexachloride ion
disodium copper tetrachloride
dipotassium antimony(III) pentachloride

40. [Pt(NH3)4][PtCl4]

tetraamminecopper(II) ion
tetraamminedichlorocobalt(III) chloride
hexachloroplatinate(IV) ion
sodium tetrachlorocuprate(II)
potassium pentachloroantimonate(III)

[Cu(NH3)4]2+
[CoCl2(NH3)4]Cl
[PtCl6]2
Na2[CuCl4]
K2[SbCl5]

tetraammineplatinum(II) tetrachloroplatinate(II)

45. The successive acid ionizations of a complex ion such as [Fe(OH)6]3+ are more nearly equal
in magnitude than those of an uncharged polyprotic acid such as H3PO4 principally because
the complex ion has a positive charge. The second proton is leaving a species which has one
fewer positive charge but which is nonetheless positively charged. Since positive charges
repel each other, successive ionizations should not show a great decrease in the magnitude
of their ionization constants. In the case of polyprotic acids, on the other hand, successive
protons are leaving a species whose negative charge is increasingly greater with each step.
Since unlike charges attract each other, it becomes increasingly difficult to remove
successive protons.
47. (a)

Fe(H 2 O)63+ (aq)

Initial 0.100 M
Equil. (0.100 x ) M

-4

K 9.0 10

H 2 O(l)

Fe(H 2 O)5 OH2 (aq)

H3 O
0M
x

0M
x

{where x is the molar quantity of Fe(H 2O)63+ (aq) hydrolyzed}

K

[[Fe(H 2 O)5 OH]2+ ] [H 3 O + ]

x2
9.0 10-4
=
0.100-x
[[Fe(H 2 O)6 ]3+ ]

Solving, we find x 9.5 103 M, which is the [H 3 O + ] so:

pH log(9.5 103 ) 2.02

(b)

[Fe(H 2 O)6 ]3+ (aq) H 2 O(l)

[Fe(H 2 O)5OH]2 (aq)

initial 0.100 M
equil.

-4

K 9.0 10

0M

(0.100 x ) M

xM

3+

{where x is [[Fe(H 2 O)6 ] ] reacting}

K

[[Fe(H 2 O)5OH]2 ] [H 3O + ] x (0.100 x)

9.0 10-4
[[Fe(H 2 O)6 ]3+ ]
(0.100-x)

Solving, we find x 9.0 10-4 M, which is the [[Fe(H 2 O)5OH]2 ]

657

H 3O
0.100 M

(0.100 x) M

Chapter 24: Complex Ions and Coordination Compounds

We simply substitute [[Fe(H 2 O)5 OH]2 ] = 1.0 10-6 M into the K a expression

(c)

with [Fe(H 2 O)6 ]3+ 0.100 M and determine the concentration of H 3 O +

[H 3 O + ]

K a [[Fe(H 2 O)6 ]3+ ] 9.0 10-4 (0.100 M)

90. M
[[Fe(H 2 O)5 OH]2 ]
[1.0 10-6 M]

To maintain the concentration at this level requires an impossibly high concentration of H 3 O +

51. If a 99% conversion to the chloro complex is achieved, which is the percent conversion
necessary to produce a yellow color, [[CuCl4]2] = 0.99 0.10 M = 0.099 M, and
[[Cu(H2O)4]2+] = 0.01 0.10 M = 0.0010 M. We substitute these values into the formation
constant expression and solve for [Cl].
Kf

[[CuCl 4 ] 2 ]
0.099 M
4.2 10 5
4
2
[[Cu(H 2 O) 4 ] ] [Cl ]
0.0010 M [Cl ] 4
4

[Cl ]

0.099
0.0010 4.2 10 5

0.12 M

This is the final concentration of free chloride ion in the solution. If we wish to account for all
chloride ion that has been added, we must include the chloride ion present in the complex ion.
total [Cl] = 0.12 M free Cl + (4 0.099 M) bound Cl = 0.52 M
52. (a)

Oxidation:

2H 2 O(l)
O2 (g) 4 H (aq) 4 e3

Reduction: {Co ((aq) e

Co (aq)}
Net:

E -1.229 V
E 1.82 V

4 Co3 (aq) 2 H2 O(l)

4 Co2 (aq) 4 H (aq) O2 (g) Ecell 0.59 V

[Co(NH3 )6 ]3 (aq)
(b) Reaction: Co3 (aq) 6 NH3 (aq)

Initial: 1.0 M
Changes: xM
Equil: (1.0 x)M

Kf

0.10 M
constant
0.10 M

0M
xM
xM

[[Co(NH 3 )6 ]3 ]
x
4.5 1033
3
6
(1.0 x)(0.10)6
[Co ][NH 3 ]

Thus [[Co(NH3)6]3+] = 1.0 M because K is so large, and

1
[Co 3 ]
2.2 10 -28 M
27
4.5 10

658

x
4.5 1027
1.0 x

Chapter 24: Complex Ions and Coordination Compounds

(c) The equilibrium and equilibrium constant for the reaction of NH3 with water follows.
NH 4 (aq) OH (aq)
NH 3 (aq) H 2 O(l)
[NH 4 ][OH - ] [OH ]2

K b 1.8 10
[NH 3 ]
0.10
5

[OH ]

0.10(1.8 105 ) 0.0013 M

In determining the [OH ], we have noted that [NH4+] = [OH ] by stoichiometry, and also that
Kw
1.0 10 14

[NH3] = 0.10 M, as we assumed above. [H 3 O ]

7.7 10 12 M

0.0013
[OH ]
We use the Nernst equation to determine the potential of reaction (24.12) at the conditions
described.
E E cell

[Co 2 ]4 [H ]4 P[O 2 ]
0.0592

log
4
[Co3 ]4

0.0592
(1 104 ) 4 (7.7 1012 ) 4 0.2
0.59 V 0.732 V 0.142 V
E 0.59
log
4
(2.2 1028 ) 4
The negative cell potential indicates that the reaction indeed does not occur.

54. We first determine [Ag+] in the cyanide solution.

[[Ag(CN) 2 ] ]
0.10
5.6 1018

[Ag ][CN ]
[Ag ] (0.10.) 2
The cell reaction is as follows. It has
0.10

18
[Ag ]
1.8 10
5.6 1018 (0.10) 2
E cell 0.000 V ; the same reaction occurs at both anode and cathode and thus the Nernstian
voltage is influenced only by the Ag+ concentration.
Kf

Ag (0.10 M)
Ag (0.10 M [Ag(CN) 2 ] , 0.10 M KCN)
E E

[Ag ]CN
0.0592
1.8 10 18
log

0.000

0.0592
log
0.99 V
1
0.10
[Ag ]

57. The Cr3+ ion would have 3 unpaired electrons, each residing in a 3d orbital and would be sp3d2
hybridized. The hybrid orbitals would be hybrids of 4s, 4p, and 3d (or 4d) orbitals. Each CrNH3
coordinate covalent bond is a bond formed when a lone pair in an sp3 orbital on N is directed
toward an empty sp3d2 orbital on Cr3+. The number of unpaired electrons predicted by valence bond
theory would be the same as the number of unpaired electrons predicted by crystal field theory.
62. The coordination compound is face-centered cubic, K+ occupies tetrahedral holes, while
PtCl62- occupies octahedral holes.

659

Chapter 24: Complex Ions and Coordination Compounds

63.

# NH3

Formula:

K2[PtCl6]

K[PtCl5(NH3)]

PtCl4(NH3)2

[PtCl3(NH3)3]Cl

Total # ions

(per formula
unit)
# NH3

Formula:

[PtCl2(NH3)4]Cl2

[PtCl(NH3)5]Cl3

[Pt(NH3)6]Cl4

Total # ions

(per formula
unit)

FEATURE PROBLEMS
64. (a) A trigonal prismatic structure predicts three geometric isomers for [CoCl2(NH3)4]+, which is
one more than the actual number of geometric isomers found for this complex ion. All three
geometric isomers arising from a trigonal prism are shown below.
Cl

Cl

Cl
Cl

Cl
Cl
(i)

(ii)

(iii)

The fact that the trigonal prismatic structure does not afford the correct number of isomers is a
clear indication that the ion actually adopts some other structural form (i.e., the theoretical model
is contradicted by the experimental result). We know now of course, that this ion has an
octahedral structure and as a result, it can exist only in cis and trans configurations.
(b) All attempts to produce optical isomers of [Co(en)3]3+ based upon a trigonal prismatic structure are
shown below. The ethylenediamine ligand appears as an arc in diagrams below:

(i)

(ii)

(iii)

Only structure (iii), which has an ethylenediamine ligand connecting the diagonal corners of a
face can give rise to optical isomers. Structure (iii) is highly unlikely, however, because the
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Chapter 24: Complex Ions and Coordination Compounds

ethylenediamine ligand is simply too short to effectively span the diagonal distance across the
face of the prism. Thus, barring any unusual stretching of the ethylenediamine ligand, a trigonal
prismatic structure cannot account for the optical isomerism that was observed for [Co(en)3]3+.

SELF-ASSESSMENT EXERCISES
70.

(d)

71.

(e)

72.

(b)

73.

(a)

74.

(d)

75.

(c)

76.

(b)

77.

(a) pentaamminebromocobalt(III)sulfate, no isomerism.

(b) hexaamminechromium(III)hexacyanocobaltate(III), no isomerism.
(c) sodiumhexanitrito-N-cobaltate(III), no isomerism
(d) tris(ethylenediamine)cobalt(III)chloride, two optical isomers.

78.

(a) [Ag(CN)2]-; (b) [Pt(NO2)(NH3)3]+; (c) [CoCl(en)2(H2O)]2+; (d) K4[Cr(CN)6]

79.
Cl

Cl
Pt

Cl

2-

H2
N

Cl

H2N

80.

Cl
Cl

Fe
O

Cl

NH2
H2N

Cl

(a)

Cl
Fe

Cl

Cl
H3N

NH3
Cr

H3N

NH3
OH

(b)

(c)

(d)

(a) one structure only (all positions are equivalent for the H2O ligand; NH3 ligands
attach at the remaining five sites).

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Chapter 24: Complex Ions and Coordination Compounds

+3
NH3
H2O

NH3
Co

H3N

NH3
NH3

(b) two structures, cis and trans, based on the placement of H2O.
+3

+3

NH3
H2O

NH3
NH3

H2O

Co
H3N

NH3
Co

OH2

H2O

NH3

NH3
NH3

trans

cis

(c) two structures, fac and mer.

+3

+3

NH3
H3N

NH3
NH3

H2O

Co
H2O

OH2
Co

OH2

H2O

OH2

NH3
NH3

fac

mer

(d) two structures, cis and trans, based on the placement of NH3.
+3

+3

NH3
H2O

OH2
OH2

H3N

Co
H2O

OH2
Co

OH2

H3N

NH3

OH2
OH2

trans

cis

81.

(a) coordination isomerism, based on the interchange of ligands between the

complex cation and complex anion.
(b) linkage isomerism, based on the mode of attachment of the SCN- ligand (either
SCN- or NCS-).
(c) no isomerism
(d) geometric isomerism, based on whether Cl- ligands are cis or trans.
(e) geometric isomerism, based on whether the NH3 or OH- ligands are fac or mer.

82.

(a) geometric isomerism (cis and trans) and optical isomerism in the cis isomer.
(b) geometric isomerism (cis and trans), optical isomerism in the cis isomer, and linkage
isomerism in the thiocyanate ligand.
(c) no isomers.

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Chapter 24: Complex Ions and Coordination Compounds

(d) no isomers for this square-planar complex.

(e) two geometric isomers, one with the tridentate ligand occupying meridional positions
and the other with the tridentate ligand occupying facial positions.
83.

Because ethylenediamine (en) is a stronger field ligand than H2O, more energy must
be absorbed by [Co(en)3]3+ than by [Co(H2O)6]3+ to simulate an electronic transition.
This means that [Co(en)3]3+(aq) absorbs shorter wavelength light and transmits longer
wavelength light than does [Co(H2O)6]3+(aq). Thus [Co(en)3]3+(aq) is yellow and
[Co(H2O)6]3+(aq) is blue.

663